EP0945404A2 - Perameisensäure und Peressigsäure enthaltendes wässriges Desinfektionsmittel, Verfahren zu dessen Herstellung und dessen Verwendung - Google Patents
Perameisensäure und Peressigsäure enthaltendes wässriges Desinfektionsmittel, Verfahren zu dessen Herstellung und dessen Verwendung Download PDFInfo
- Publication number
- EP0945404A2 EP0945404A2 EP99105641A EP99105641A EP0945404A2 EP 0945404 A2 EP0945404 A2 EP 0945404A2 EP 99105641 A EP99105641 A EP 99105641A EP 99105641 A EP99105641 A EP 99105641A EP 0945404 A2 EP0945404 A2 EP 0945404A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- weight
- formic acid
- hydrogen peroxide
- disinfectant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 239000000645 desinfectant Substances 0.000 title claims abstract description 44
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims description 12
- 238000002360 preparation method Methods 0.000 title claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 83
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 62
- 235000019253 formic acid Nutrition 0.000 claims abstract description 42
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000002253 acid Substances 0.000 claims abstract description 14
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 13
- 239000011707 mineral Substances 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 239000004280 Sodium formate Substances 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims abstract description 10
- 235000019254 sodium formate Nutrition 0.000 claims abstract description 10
- -1 Formic acid ester Chemical class 0.000 claims abstract description 9
- 239000008346 aqueous phase Substances 0.000 claims abstract description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000004659 sterilization and disinfection Methods 0.000 claims description 9
- 244000005700 microbiome Species 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 241000894006 Bacteria Species 0.000 claims description 5
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 5
- 230000009182 swimming Effects 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 241000195493 Cryptophyta Species 0.000 claims description 3
- 241000700605 Viruses Species 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 241000233866 Fungi Species 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 claims description 2
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 2
- 229940005657 pyrophosphoric acid Drugs 0.000 claims description 2
- XVVLAOSRANDVDB-UHFFFAOYSA-N formic acid Chemical compound OC=O.OC=O XVVLAOSRANDVDB-UHFFFAOYSA-N 0.000 claims 1
- 229910001415 sodium ion Inorganic materials 0.000 claims 1
- 230000003641 microbiacidal effect Effects 0.000 abstract description 7
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 abstract 1
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 42
- SCKXCAADGDQQCS-UHFFFAOYSA-N Performic acid Chemical compound OOC=O SCKXCAADGDQQCS-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 229940044170 formate Drugs 0.000 description 5
- 230000001580 bacterial effect Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 150000002927 oxygen compounds Chemical class 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000003385 bacteriostatic effect Effects 0.000 description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000001311 chemical methods and process Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 230000035784 germination Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000010841 municipal wastewater Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 150000004965 peroxy acids Chemical class 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 235000001674 Agaricus brunnescens Nutrition 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- CBOCVOKPQGJKKJ-UHFFFAOYSA-L Calcium formate Chemical compound [Ca+2].[O-]C=O.[O-]C=O CBOCVOKPQGJKKJ-UHFFFAOYSA-L 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 241000589516 Pseudomonas Species 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003808 active oxygen stabilizer Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 1
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 230000029918 bioluminescence Effects 0.000 description 1
- 238000005415 bioluminescence Methods 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000004281 calcium formate Substances 0.000 description 1
- 235000019255 calcium formate Nutrition 0.000 description 1
- 229940044172 calcium formate Drugs 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 235000013365 dairy product Nutrition 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- HQVFCQRVQFYGRJ-UHFFFAOYSA-N formic acid;hydrate Chemical compound O.OC=O HQVFCQRVQFYGRJ-UHFFFAOYSA-N 0.000 description 1
- 150000004674 formic acids Chemical class 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229940124561 microbicide Drugs 0.000 description 1
- 210000003097 mucus Anatomy 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical class OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
Definitions
- the invention is directed to performic acid and Aqueous disinfectant containing peracetic acid, a process for its production and its use for controlling microorganisms, especially in aqueous Systems.
- Disinfectant means an agent that is suitable for controlling all types of microorganisms, such as bacteria, viruses, fungi and algae; in addition, this agent is suitable for controlling small organisms, such as zooplankton.
- peroxyacetic acid is a highly effective agent, the use of which enables rapid germ reduction. Accordingly, peracetic acid is used, among other things, for sterilization in the food industry, bottle and hospital disinfection.
- Commercially available peracetic acid solutions with a content of 15% by weight of PES additionally contain about 14% by weight of H 2 O 2 and 28% by weight of acetic acid.
- the use of such PES solutions creates handling, storage, material and transport problems because of their unpleasant caustic and fire-promoting properties.
- Another disadvantage is the high acetic acid content, which can lead to an increased COD content and, in addition, to drastic recontamination.
- the PAS solution according to WO 94/20424 and EP 0 231 632 is generated in situ by reacting hydrogen peroxide with formic acid, the molar ratio of H 2 O 2 to formic acid being in the range from 1:10 to 10: 1. Highly concentrated formic acid and 20 to 50% by weight hydrogen peroxide are used. Disadvantages of such a PAS solution are the not inconsiderable risk of explosion and the high level of corrosiveness and thus handling and safety problems.
- a disinfectant containing performic acid also known from WO 95/32625: The Performic acid by reacting a formic acid ester, such as ethyl formate, with an oxidizing agent, in particular Hydrogen peroxide.
- a formic acid ester such as ethyl formate
- an oxidizing agent in particular Hydrogen peroxide.
- the advantage over the System formic acid / hydrogen peroxide lower Corrosiveness, however, the evidence of the disadvantage Examples of very low concentration of performic acid, whereby only after a longer period of exposure sufficient kill rate is achievable.
- DE-A 39 29 335 describes a method for disinfection taught by textiles in car washes, the last Rinse agent containing peroxycarboxylic acid is added.
- the agent is in particular to an equilibrium peroxycarboxylic acid solution with a Content of 40 to 60% by weight carboxylic acid, 2 to 5% by weight Peroxycarboxylic acid and 0.1 to 3 wt .-% hydrogen peroxide.
- Acetic acid also formic acid and propionic acid as well Mixtures of such acids are used; Details on two Carboxylic acids and, accordingly, the corresponding ones Agents containing peroxycarboxylic acids can be Do not remove the document.
- the object of the invention is accordingly a performic acid, peracetic acid and hydrogen peroxide containing disinfectant that is easy and manufactured safely in situ and after a short time Response time can be used for disinfection purposes can.
- the disinfectant should be after a short time Exposure time to a high kill rate of Lead microorganisms in aqueous systems.
- a process for the production of a Aqueous containing peracetic acid and performic acid Disinfectant by adding a source for Formic acid to a hydrogen peroxide containing aqueous phase, which is characterized in that as Source of formic acid or formic acid water soluble salt of formic acid in an amount of 0.1 to 1.0 mole of formic acid or 0.1 to 1.0 equivalent Formate per kg of disinfectant to be produced and as the aqueous phase containing hydrogen peroxide Equilibrium peracetic acid solution containing 20 up to 60% by weight hydrogen peroxide, 0.5 to 6% by weight Peracetic acid, less than 10% by weight, especially less than 2% by weight of acetic acid and up to 3% by weight of one Mineral acid is used and the mixture before use at least 1 minute to 5 hours.
- an equilibrium peracetic acid is used as the aqueous phase containing hydrogen peroxide and peracetic acid, which also contains acetic acid due to the equilibrium.
- the equilibrium peracetic acid expediently also contains a mineral acid catalyst from its production, such as, in particular, one from the series consisting of sulfuric acid, phosphoric acid (H 3 PO 4 ), pyrophosphoric acid (H 4 P 2 O 7 ) and polyphosphoric acid (H n + z PnO 3n +1 ), where n is an integer ⁇ 3.
- the peracetic acid solution expediently contains 0.1 to 5% by weight, in particular 0.5 to 3% by weight, of mineral acid.
- the content of peracetic acid (PES) in the equilibrium peracetic acid to be used is expediently in the range from 0.5 to 15% by weight, in particular 0.5 to 6% by weight and, in a further preferred embodiment, in the range from approximately 1 to 3% by weight .-%.
- Such equilibrium peracetic acid solutions generally have a hydrogen peroxide content in the range from about 20 to 60% by weight, in particular 20 to 50% by weight; preferred solutions with 1 to 3% by weight of peracetic acid usually contain 30 to 50% by weight of hydrogen peroxide.
- the acetic acid content of preferred equilibrium peracetic acid solutions should generally be below 10% by weight. Solutions with 0.5 to 3% by weight of PES preferably contain less than 2% by weight and particularly preferably less than 1% by weight of acetic acid.
- an equilibrium peracetic acid containing 30 to 50% by weight of H 2 O 2 , 1 to 3% by weight of peracetic acid (PES) is used as the aqueous phase, less than 2% by weight, in particular less than 1 wt .-% acetic acid, and 0.5 to 3 wt .-% mineral acid used.
- PES peracetic acid
- Either formic acid, a lower formic acid ester, such as methyl, ethyl or propyl formate, or a water-soluble salt of formic acid can be used as the source of formic acid.
- the salt can be added in the solid state or in the form of an aqueous solution of the aqueous phase containing H 2 O 2 and PES.
- Water-soluble salts are alkali metal formates, especially sodium formate, and alkaline earth metal formates, especially calcium formate.
- Ammonium formate and quaternary ammonium formates can also be used, it being possible for the quaternary ammonium ion, for example (C 10 -C 18 ) alkyltrimethylammonium, to itself have microbicidal properties.
- the particular advantage of using an alkali metal formate is the safe and easy handling, the absence of odor in the salt and the reduction in the corrosiveness of the disinfectant to be produced.
- the amount of formic acid or salt thereof is used usually in the range of 0.1 to 1 mole of formic acid or 0.1 to 1 equivalent of formate per kg of disinfectant to be produced. If the peracetic acid solution used a sufficiently large Contains amount of mineral acid, the amount used can also the use of formats can be further increased. At the Use of a formic acid salt is said to be the amount used lower than to neutralize those present Mineral acid is required. Are preferred per equivalent mineral acid present 0.1 to 0.8 equivalents of alkali metal formate, in particular Sodium formate.
- the solution now containing performic acid (PAS), peracetic acid (PES) and hydrogen peroxide can be used as a disinfectant.
- PAS performic acid
- PES peracetic acid
- hydrogen peroxide can be used as a disinfectant.
- the solution containing PAS should preferably be used within about 12 hours, since the PAS content decreases again after reaching a maximum value and the peracid content essentially drops again to the values of the solution originally used.
- the available aqueous disinfectant contains per kg: 0.1 to 3% by weight performic acid, 0.1 to 5% by weight Peracetic acid, formic acid and acetic acid in one Total amount less than 10% by weight and 20 to 50% by weight Hydrogen peroxide.
- the disinfectant can be common Additives, including active oxygen stabilizers, such as Complexing agents from the series of phosphonic acid compounds, Tin compounds and pyridinecarboxylic acids or salts thereof or contain radical scavengers, furthermore corrosion inhibitors, Hardness stabilizers, deposit inhibitors and surfactants, especially anionic and nonionic surfactants.
- active oxygen stabilizers such as Complexing agents from the series of phosphonic acid compounds, Tin compounds and pyridinecarboxylic acids or salts thereof or contain radical scavengers, furthermore corrosion inhibitors, Hardness stabilizers, deposit inhibitors and surfactants, especially anionic and nonionic surfactants.
- microbicides from others can also be used Classes of substances should be present as active oxygen compounds.
- the disinfectants obtainable according to the invention are characterized by their high effectiveness when fighting of microorganisms from the range of bacteria, viruses, Mushrooms and algae. Already within 30 seconds Add the disinfectant to an aqueous system the bacterial count [CFU / ml] drops by 3 to 4 powers of ten. A such a high and especially rapid killing rate is at Use of a disinfectant in the swimming pool area required due to legal requirements. Obviously acts a PAS and PES containing invention Disinfectant solution, based on the entire Percarboxylic acid content, better than a conventional one Solution containing only PAS as percarboxylic acid.
- Example B2 As from the Example B2 and the comparative examples VB2 and VB0 emerges, was with the solution of the invention achieved faster and more complete bacterial reduction than with a previously known as percarboxylic acid only Solution containing performic acid. This was surprising because the total percarboxylic acid content in Example 2 only was about 40% of that of Comparative Example 2. Though Example B2 contained more hydrogen peroxide than that Comparative example VB2, however, it is known that Hydrogen peroxide is bacteriostatic, but hardly has a bactericidal effect.
- the amount of disinfectant used depends on the intended purpose. Usually 1 to 1000 mg, in particular 1 to 100 mg and particularly preferably 5 to 20 mg of disinfectant per 1 to be treated Water used.
- the inventive method can be in apply different areas. Be exemplary called: circulating water and waste water from food, Brewing and dairy industries; Circulation and waste water chemical processes in which there is no disinfection and / or inhibition of germ growth can lead to problems - Mucus and odor formation; Water and sludge petrochemical and municipal wastewater treatment plants; swimming pool water.
- Another application of the The inventive method is in the range Soil remediation: By adding the disinfectant in the water of an infiltration well Reduced microorganisms in the immediate vicinity of the same; the biological decomposition of the as Oxygen carrier present hydrogen peroxide reduced and a wider range of undecomposed Hydrogen peroxide reached in the soil.
- the main advantages of the method according to the invention are the safe handling and rapid availability of the Performic acid from easily transportable and storable Fabrics.
- Sodium formate as a source of formic acid is in the Easier to transport compared to formic acids, storable, odorless and non-corrosive.
- the disinfectant effect can be determined by the amount used the source of formic acid and composition of the Easily control the peracetic acid solution to be used. Another advantage is the rapid effect and the high Germination rate. Solutions with very low Acetic acid content are characterized by delayed Recontamination.
- the invention Disinfectant is particularly suitable where one too high acidity is undesirable.
- the concentration of after the preparation of the agent according to the invention Performic acid drops again after a few hours, while the effect of the peracetic acid contained in the agent largely preserved.
- the agent is therefore suitable especially where there is initially an increased effect, but at the same time a longer-lasting microbiocide Effect is required.
- a disinfectant according to the invention was produced by adding 20 g of formic acid (AS) to 980 g of an equilibrium peracetic acid which contains 2% by weight of peracetic acid (PES), 1% by weight of acetic acid (ES) and 48% by weight of hydrogen peroxide, and 2% by weight .-% H 2 SO 4 contained.
- this solution as a disinfectant compared to the one used Equilibrium peracetic acid for the treatment of swimming pool water used; Use 10 mg each Disinfectant per 1 water.
- the table shows the results -% AO from peracids as a function of time. for comparison B 3 B 4 Time (h) G-PES 2 G-PES 2 + 1% AS G-PES 2 + 1% Nafo 0 0.42 1 0.45 3rd 0.52 4th 0.48 5 0.62 6 0.50 7 0.47 65 0.42 0.50 0.43
- G-PES 5 5% by weight equilibrium peracetic acid solution
- AS Formic acid
- Nafo sodium formate
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Beispiel 1 | Vergleichsbeispiel 1 | |
Keimtötungsgeschwindigkeit | 22 - 30 Sekunden | größer 60 Sekunden |
Pseudomonas aernginosa ATCI 15442 | 4 log-Stufen | 4 log-Stufen |
Escherichia coli ATCI 11229 | 3 log-Stufen | 3 log-Stufen |
B 2 | VB 2 | |
Herstellung | Mischen einer 2 Gew.-% PES, 48 Gew.-% H2O2, 1 Gew. -% ES und 2 Gew.-% H2SO4 enthaltenden Peressigsäurelösung (= VB 0) 3 Gew.-% HCOOH (AS) ; 4 h stehen lassen | Mischen von 68 g einer 35 gew.-%igen H2O2-Lösung mit 32 g Ameisensäure (AS) ; 4 h stehen lassen |
Zusammensetzung (in Gew.-%) | ||
PAS | 1,55 | 8,0 |
PES | 1,90 | - |
AS | 1,85 | 27,1 |
ES | 1,0 | - |
H2O2 | 45,1 | 19,6 |
RLU nach Minuten | B 2 | VB 2 | VB 0 |
5 | 320 | 270 | 950 |
10 | 40 | 160 | 560 |
15 | 25 | 150 | |
30 | 0 | 50 | 110 |
zum Vergleich | B 3 | B 4 | |
Zeit (h) | G-PES 2 | G-PES 2 + 1 % AS | G-PES 2 + 1 % Nafo |
0 | 0,42 | ||
1 | 0,45 | ||
3 | 0,52 | ||
4 | 0,48 | ||
5 | 0,62 | ||
6 | 0,50 | ||
7 | 0,47 | ||
65 | 0,42 | 0,50 | 0,43 |
zum Vergleich | B 5 | B 6 | |
Zeit (h) | G-PES 5 | G-PES 5 + 1 % AS | G-PES 5 + 1 % Nafo |
0 | 1,05 | ||
4 | 1,15 | ||
6 | 1,13 | 1,13 | |
8 | 1,05 | ||
65 | 1,05 | 1,07 | 1,03 |
Claims (7)
- Verfahren zur Herstellung eines Peressigsäure und Perameisensäure enthaltenden wäßrigen Desinfektionsmittels durch Zugabe einer Quelle für Ameisensäure zu einer Wasserstoffperoxid enthaltenden wäßrigen Phase,
dadurch gekennzeichnet,
daß man als Quelle für Ameisensäure Ameisensäure oder ein wasserlösliches Salz der Ameisensäure in einer Menge von 0,1 bis 1,0 Mol Ameisensäure oder 0,1 bis 1,0 Äquivalent Formiat pro kg des herzustellenden Desinfektionsmittels und als Wasserstoffperoxid enthaltende wäßrige Phase eine Gleichgewichtsperessigsäurelösung mit einem Gehalt von 20 bis 60 Gew.-% Wasserstoffperoxid, 0,5 bis 6 Gew.-% Peressigsäure, weniger als 10 Gew.-%, insbesondere weniger als 2 Gew.-% Essigsäure und bis zu 3 Gew.-% einer Mineralsäure verwendet und das Gemisch vor der Verwendung mindestens 1 Minute bis 5 Stunden stehen läßt. - Verfahren nach Anspruch 1,
dadurch gekennzeichnet,
daß man als Quelle für Ameisensäure ein Alkalimetallformiat, insbesondere Natriumformiat, verwendet und pro mÄquivalent anwesender Mineralsäure 0,1 bis 0,8 mÄquivalent Formiat zugibt. - Verfahren nach Anspruch 1 oder 2,
dadurch gekennzeichnet,
daß man eine Gleichgewichtsperessigsäure verwendet, deren Mineralsäure ausgewählt ist aus der Reihe Schwefelsäure, Phosphorsäure, Pyrophosphorsäure und Polyphosphorsäure. - Wäßriges Desinfektionsmittel,
dadurch gekennzeichnet,
daß es 0,1 bis 3 Gew.-% Perameisensäure, 0,1 bis 5 Gew.-% Peressigsäure, Ameisensäure und Essigsäure in einer Gesamtmenge von bis zu 10 Gew.-%, vorzugsweise weniger als 2 Gew.-%, Wasserstoffperoxid in einer Menge von 20 bis 50 Gew.-% und eine Mineralsäure in einer Menge von bis zu 3 Gew.-% enthält. - Wäßriges Desinfektionsmittel nach Anspruch 4,
dadurch gekennzeichnet,
daß es bis zu 1 Gew.-% Natriumionen aus bei der Herstellung eingesetztem Natriumformiat enthält. - Verwendung des wäßrigen Desinfektionsmittels gemäß Anspruch 4 oder 5 zum Bekämpfen von Mikroorganismen aus der Reihe der Bakterien, Viren, Pilze und Algen in wäßrigen Systemen und auf Oberflächen.
- Verwendung nach Anspruch 6,
dadurch gekennzeichnet,
daß man das Mittel zur Desinfektion von Schwimmbadwasser verwendet.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19812589 | 1998-03-23 | ||
DE19812589A DE19812589A1 (de) | 1998-03-23 | 1998-03-23 | Perameisensäure enthaltendes wäßriges Desinfektionsmittel, Verfahren zu dessen Herstellung und deren Verwendung |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0945404A2 true EP0945404A2 (de) | 1999-09-29 |
EP0945404A3 EP0945404A3 (de) | 2000-01-26 |
EP0945404B1 EP0945404B1 (de) | 2002-11-13 |
Family
ID=7861904
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP99105641A Expired - Lifetime EP0945404B1 (de) | 1998-03-23 | 1999-03-19 | Perameisensäure und Peressigsäure enthaltendes wässriges Desinfektionsmittel, Verfahren zu dessen Herstellung und dessen Verwendung |
Country Status (9)
Country | Link |
---|---|
US (1) | US6211237B1 (de) |
EP (1) | EP0945404B1 (de) |
JP (1) | JPH11322523A (de) |
AT (1) | ATE227695T1 (de) |
BR (1) | BR9900604A (de) |
CA (1) | CA2266523C (de) |
DE (2) | DE19812589A1 (de) |
ES (1) | ES2184364T3 (de) |
ZA (1) | ZA992230B (de) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2153720A1 (de) * | 2008-08-06 | 2010-02-17 | LANXESS Distribution GmbH | Formiathaltig Fungizide Mischungen |
WO2022015142A1 (es) * | 2020-07-13 | 2022-01-20 | Centro De Retina Médica Y Quirúrgica, S.C. | Formulación a base de ácido peracético asociada a un proceso de trituración, cuya combinación transforma los cultivos y cepas de residuos peligrosos biológico-infecciosos generados en la producción de vacunas in ovo a materia prima para la fabricación de compostas de alto contenido protéico |
Families Citing this family (37)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6955766B2 (en) * | 1999-11-24 | 2005-10-18 | Degussa Ag | Method for reducing harmful organisms in currents of water |
FI116560B (fi) * | 2001-06-19 | 2005-12-30 | Kemira Oyj | Puunkäsittelyliuos ja menetelmä puun säilyvyyden parantamiseksi |
US7045153B2 (en) * | 2003-06-27 | 2006-05-16 | Enviro Tech Chemical Services, Inc. | Highly concentrated bromine compositions and methods of preparation |
US20070249712A1 (en) * | 2005-02-04 | 2007-10-25 | Dee Alejandro O | Peracetic teat dip |
FI118735B (fi) * | 2005-09-13 | 2008-02-29 | Kemira Oyj | Menetelmä peroksihappojen valmistamiseksi |
FI119800B (fi) * | 2006-11-09 | 2009-03-31 | Kemira Oyj | Menetelmä mikro-organismien kasvun estämiseksi ja mikro-organismien kasvua estävä yhdistelmä |
CN101821385A (zh) * | 2007-05-10 | 2010-09-01 | 丹尼斯科美国公司 | 稳定的酶促过酸产生系统 |
US8871807B2 (en) | 2008-03-28 | 2014-10-28 | Ecolab Usa Inc. | Detergents capable of cleaning, bleaching, sanitizing and/or disinfecting textiles including sulfoperoxycarboxylic acids |
US12203056B2 (en) | 2008-03-28 | 2025-01-21 | Ecolab Usa Inc. | Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents |
US8809392B2 (en) | 2008-03-28 | 2014-08-19 | Ecolab Usa Inc. | Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents |
BRPI0907918B1 (pt) | 2008-03-28 | 2018-07-24 | Ecolab Inc. | Ácidos sulfoperoxicarboxílicos, sua preparação e métodos de utilizção como agentes alvejantes e antimicrobianos |
US20090304608A1 (en) * | 2008-06-05 | 2009-12-10 | Innovasource, Llc | Aqueous Hydrogen Peroxide Solution for Use as a Disinfectant or Anti-Microbial Personal Care Product |
EP2615932B1 (de) | 2010-09-14 | 2021-09-08 | Pimi Agro Cleantech Ltd. (Israel) | Verfahren zur bearbeitung eines essbaren materials und substrate dafür |
US8933263B2 (en) | 2010-12-29 | 2015-01-13 | Ecolab Usa Inc. | Water temperature as a means of controlling kinetics of onsite generated peracids |
US9321664B2 (en) | 2011-12-20 | 2016-04-26 | Ecolab Usa Inc. | Stable percarboxylic acid compositions and uses thereof |
PL2609990T3 (pl) * | 2011-12-30 | 2022-11-14 | Kemira Oyj | Sposób zapobiegania wzrostowi drobnoustrojów na membranie filtracyjnej |
EP2831000A4 (de) | 2012-03-30 | 2016-03-30 | Ecolab Usa Inc | Verwendung von peressigsäure/wasserstoffperoxid und peroxidreduzierungsmitteln zur behandlung von bohrflüssigkeiten, fracking-flüssigkeiten, rückflusswasser und entsorgungswasser |
FI124326B (en) * | 2012-05-25 | 2014-06-30 | Kemira Oyj | Method for treating biomass |
US20140256811A1 (en) | 2013-03-05 | 2014-09-11 | Ecolab Usa Inc. | Efficient stabilizer in controlling self accelerated decomposition temperature of peroxycarboxylic acid compositions with mineral acids |
US10165774B2 (en) | 2013-03-05 | 2019-01-01 | Ecolab Usa Inc. | Defoamer useful in a peracid composition with anionic surfactants |
US8822719B1 (en) | 2013-03-05 | 2014-09-02 | Ecolab Usa Inc. | Peroxycarboxylic acid compositions suitable for inline optical or conductivity monitoring |
CA2971416C (en) * | 2014-12-18 | 2024-01-23 | Ecolab Usa Inc. | Methods for forming peroxyformic acid and uses thereof |
US11040902B2 (en) | 2014-12-18 | 2021-06-22 | Ecolab Usa Inc. | Use of percarboxylic acids for scale prevention in treatment systems |
CA2971411C (en) | 2014-12-18 | 2022-03-22 | Ecolab Usa Inc. | Generation of peroxyformic acid through polyhydric alcohol formate |
EP3328197A1 (de) * | 2015-07-31 | 2018-06-06 | Performance Packaging Of Nevada Llc | Verfahren zur sterilisation und/oder desinfektion |
US10172351B2 (en) | 2015-09-04 | 2019-01-08 | Ecolab Usa Inc. | Performic acid on-site generator and formulator |
WO2017044806A1 (en) | 2015-09-10 | 2017-03-16 | Ecolab Usa Inc. | Self indicating antimicrobial chemistry |
BR112018007928A2 (pt) * | 2015-11-12 | 2018-10-30 | Ecolab Usa Inc. | método para inibir corrosão, e, composição. |
MX2018007422A (es) | 2015-12-16 | 2018-08-15 | Ecolab Usa Inc | Composiciones de acido peroxiformico para limpieza por filtracion en membrana. |
ES2948966T3 (es) | 2016-04-15 | 2023-09-22 | Ecolab Usa Inc | Prevención de biopelícula con ácido perfórmico para lavadores químicos industriales de CO2 |
BR112019010464B1 (pt) | 2016-12-15 | 2024-02-06 | Ecolab Usa Inc | Método para remover micro-organismos e depósitos minerais em um sistema de membrana |
CA3091989A1 (en) * | 2018-04-19 | 2019-10-24 | Chemtreat, Inc. | Methods and systems for monitoring peroxyacid content in a fluid |
MX2018006182A (es) * | 2018-05-18 | 2019-11-19 | Centro De Retina Medica Y Quirurgica S C | Formulación de acido paracetico para la eliminación de virus en residuos peligrosos biologicos infecciosos en desechos hospitalarios. |
AU2019285304B2 (en) | 2018-06-15 | 2021-10-14 | Ecolab Usa Inc. | On site generated performic acid compositions for teat treatment |
US12058999B2 (en) | 2018-08-22 | 2024-08-13 | Ecolab Usa Inc. | Hydrogen peroxide and peracid stabilization with molecules based on a pyridine carboxylic acid |
US12096768B2 (en) | 2019-08-07 | 2024-09-24 | Ecolab Usa Inc. | Polymeric and solid-supported chelators for stabilization of peracid-containing compositions |
CN116616290A (zh) * | 2023-04-10 | 2023-08-22 | 上海利康生物高科技有限公司 | 一种低残留过氧化氢消毒剂及其制备方法 |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL7608265A (nl) * | 1975-08-16 | 1977-02-18 | Henkel & Cie Gmbh | Bij opslag stabiele concentraten van functionele middelen. |
GB8531384D0 (en) | 1985-12-20 | 1986-02-05 | Unilever Plc | Sanitizing process |
JPS63277644A (ja) * | 1987-05-11 | 1988-11-15 | Mitsubishi Gas Chem Co Inc | p−アセトキシ安息香酸の製造方法 |
JPH01153791A (ja) * | 1987-12-11 | 1989-06-15 | Nippon Peroxide Co Ltd | 水溶性切削油剤の腐敗防止剤 |
DE3929335A1 (de) * | 1989-09-04 | 1991-03-07 | Henkel Kgaa | Verfahren zur desinfektion von textilien in waschstrassen |
NL9300445A (nl) | 1993-03-12 | 1994-10-03 | Kemira Peroxides Bv | Werkwijze voor het ontsmetten van water zoals "drain water" in de tuinbouw, alsmede daarbij toe te passen inrichting. |
US5409713A (en) * | 1993-03-17 | 1995-04-25 | Ecolab Inc. | Process for inhibition of microbial growth in aqueous transport streams |
DE69418903T2 (de) | 1994-03-09 | 1999-12-02 | Kemira Chemicals B.V., Europoort-Rotterdam | Verfahren zur herstellung wässeriger perameisensäurelösungen und deren verwendung |
US5616616A (en) | 1994-06-01 | 1997-04-01 | Minntech Corporation | Room Temperature sterilant |
GB9626711D0 (en) * | 1996-12-23 | 1997-02-12 | Procter & Gamble | Hair colouring compositions |
-
1998
- 1998-03-23 DE DE19812589A patent/DE19812589A1/de not_active Withdrawn
-
1999
- 1999-03-19 EP EP99105641A patent/EP0945404B1/de not_active Expired - Lifetime
- 1999-03-19 ES ES99105641T patent/ES2184364T3/es not_active Expired - Lifetime
- 1999-03-19 DE DE59903367T patent/DE59903367D1/de not_active Expired - Lifetime
- 1999-03-19 AT AT99105641T patent/ATE227695T1/de active
- 1999-03-19 ZA ZA9902230A patent/ZA992230B/xx unknown
- 1999-03-22 CA CA002266523A patent/CA2266523C/en not_active Expired - Fee Related
- 1999-03-23 BR BR9900604-9A patent/BR9900604A/pt not_active Application Discontinuation
- 1999-03-23 US US09/274,342 patent/US6211237B1/en not_active Expired - Fee Related
- 1999-03-23 JP JP11078606A patent/JPH11322523A/ja not_active Ceased
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2153720A1 (de) * | 2008-08-06 | 2010-02-17 | LANXESS Distribution GmbH | Formiathaltig Fungizide Mischungen |
WO2010015635A3 (de) * | 2008-08-06 | 2011-01-06 | Lanxess Distribution Gmbh | Formiathaltig fungizide mischungen |
WO2022015142A1 (es) * | 2020-07-13 | 2022-01-20 | Centro De Retina Médica Y Quirúrgica, S.C. | Formulación a base de ácido peracético asociada a un proceso de trituración, cuya combinación transforma los cultivos y cepas de residuos peligrosos biológico-infecciosos generados en la producción de vacunas in ovo a materia prima para la fabricación de compostas de alto contenido protéico |
Also Published As
Publication number | Publication date |
---|---|
EP0945404B1 (de) | 2002-11-13 |
CA2266523C (en) | 2008-05-20 |
EP0945404A3 (de) | 2000-01-26 |
CA2266523A1 (en) | 1999-09-23 |
DE19812589A1 (de) | 1999-10-07 |
BR9900604A (pt) | 2000-06-27 |
DE59903367D1 (de) | 2002-12-19 |
US6211237B1 (en) | 2001-04-03 |
JPH11322523A (ja) | 1999-11-24 |
ES2184364T3 (es) | 2003-04-01 |
ZA992230B (en) | 1999-09-29 |
ATE227695T1 (de) | 2002-11-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0945404B1 (de) | Perameisensäure und Peressigsäure enthaltendes wässriges Desinfektionsmittel, Verfahren zu dessen Herstellung und dessen Verwendung | |
EP0851842B1 (de) | Verfahren zur desinfektion wässriger lösungen | |
DE69418305T2 (de) | Zusammensetzungen und verwendungen davon | |
DE69223628T2 (de) | Persaure antimikrobische mittel | |
DE69315762T2 (de) | Chlordioxyd freisetzende feste Zusammensetzungen | |
DE3543500C2 (de) | ||
DE69511432T2 (de) | Wässrige lösung auf basis von h202, säuren und ag, verfahren zur herstellung und verwendung auf dem gebiet der desinfektion,der hygiene und/oder der beseitigung von verschmutzung | |
DE69404286T2 (de) | Verfahren zur entkeimung von wasser, wie z.b. von giesswasser im gartenbau, sowie geraet zur durchfuehrung dieses verfahren | |
EP0945405B1 (de) | Härtestabilisierende Percarbonsäurelösungen, Verfahren zu deren Herstellung und deren Verwendung | |
DE3030476A1 (de) | Verfahren zur desinfektion eines bakterien enthalt enden waessrigen mediums | |
EP0059978B1 (de) | Verfahren zur chemischen Aufbereitung und Entkeimung von Wässern und Wassersystemen | |
EP0971583B1 (de) | Desinfektionsverfahren | |
DE2629081A1 (de) | Germizides mittel | |
EP0136309B1 (de) | Verfahren zur herstellung einer modifizierten wässrigen chloritlösung, die danach hergestellte lösung sowie deren verwendung | |
DE1617236B2 (de) | Germicide detergentien | |
EP1006085A2 (de) | Verfahren zur Schwimmbadwasseraufbereitung | |
DE69728911T2 (de) | Verfahren zur bekämpfung von mikroorganismen | |
EP1389908A1 (de) | Entkeimung von oberflächen | |
DE912798C (de) | Verfahren zur Reinigung von zirkulierendem Schwimmbeckenwasser | |
DE19642127A1 (de) | Verfahren zur Desinfektion und Mittel zu seiner Durchführung | |
EP0934084B1 (de) | Verwendung einer wässrigen chloritlösung zur desinfektion in der ernährungsindustrie | |
DE10309425B4 (de) | Mikrobizid zur Desinfektion von industriellen Wasserkreisläufen | |
EP3993627B1 (de) | Anwendungsfertiges desinfektionsmittel | |
EP1627646B1 (de) | Reinigungs- und Desinfektionsmittel für medizinische Instrumente mit verbesserter Wirksamkeit gegen Hepatitis-B-Viren | |
DE19703413C1 (de) | Körniges Filtermaterial für Flüssigkeiten |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): AT BE DE ES FI FR GB IT NL SE |
|
AX | Request for extension of the european patent |
Free format text: AL;LT;LV;MK;RO;SI |
|
PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE |
|
AX | Request for extension of the european patent |
Free format text: AL;LT;LV;MK;RO;SI |
|
RIC1 | Information provided on ipc code assigned before grant |
Free format text: 7C 02F 1/72 A |
|
17P | Request for examination filed |
Effective date: 20000119 |
|
AKX | Designation fees paid |
Free format text: AT BE DE ES FI FR GB IT NL SE |
|
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: DEGUSSA AG |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
17Q | First examination report despatched |
Effective date: 20020528 |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE DE ES FI FR GB IT NL SE |
|
REF | Corresponds to: |
Ref document number: 227695 Country of ref document: AT Date of ref document: 20021115 Kind code of ref document: T |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D Free format text: NOT ENGLISH |
|
REF | Corresponds to: |
Ref document number: 59903367 Country of ref document: DE Date of ref document: 20021219 |
|
GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) |
Effective date: 20030205 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2184364 Country of ref document: ES Kind code of ref document: T3 |
|
ET | Fr: translation filed | ||
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed |
Effective date: 20030814 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: CJ Ref country code: FR Ref legal event code: CD Ref country code: FR Ref legal event code: CA |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: TD Effective date: 20100223 Ref country code: NL Ref legal event code: SD Effective date: 20100223 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 20110314 Year of fee payment: 13 Ref country code: AT Payment date: 20110314 Year of fee payment: 13 Ref country code: FR Payment date: 20110404 Year of fee payment: 13 Ref country code: NL Payment date: 20110316 Year of fee payment: 13 Ref country code: FI Payment date: 20110314 Year of fee payment: 13 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20110325 Year of fee payment: 13 Ref country code: DE Payment date: 20110325 Year of fee payment: 13 Ref country code: BE Payment date: 20110311 Year of fee payment: 13 Ref country code: GB Payment date: 20110321 Year of fee payment: 13 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20110328 Year of fee payment: 13 |
|
BERE | Be: lapsed |
Owner name: EVONIK *DEGUSSA G.M.B.H. Effective date: 20120331 |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: V1 Effective date: 20121001 |
|
REG | Reference to a national code |
Ref country code: SE Ref legal event code: EUG |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20120320 Ref country code: FI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20120319 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20120319 |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MM01 Ref document number: 227695 Country of ref document: AT Kind code of ref document: T Effective date: 20120319 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20121130 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 59903367 Country of ref document: DE Effective date: 20121002 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20120402 Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20120319 Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20120331 Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20120319 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20120319 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20121001 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20130710 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20120320 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20121002 |